High-frequency hearing in phocid and otariid pinnipeds: an interpretation based on inertial and cochlear constraints (L)

Audiograms in air and underwater, determined by previous workers for four pinniped species, two eared seals (Otariidae) and two phocids (Phocidae), are supplemented here by measurements on their middle ear ossicular mass, enabling mechanistic interpretations of high-frequency hearing and audiogram differences. Otariid hearing is not largely affected by the medium (air/water). This indicates that cochlear constraints limit high-frequency hearing in otariids. Phocids, however, have massive middle ear ossicles, and underwater hearing has radically shifted towards higher frequencies. This suggests that the high-frequency hearing of phocids in air is constrained by ossicle inertia.     

Amorphous ice: stepwise formation of very-high-density amorphous ice from low-density amorphous ice at 125 K

On compressing low-density amorphous ice (LDA) at 125 K up to 1.6 GPa, two distinct density steps accompanied by heat evolution are observable in pressure-density curves. Samples recovered to 77 K and 1 bar after the first and second steps show the x-ray diffraction pattern of high-density amorphous ice (HDA) and very HDA (VHDA), respectively. The compression of the once formed HDA takes place linearly in density up to 0.95 GPa, where nonlinear densification and HDA --> VHDA conversion is initiated. This implies a stepwise formation process LDA--> HDA --> VHDA at 125 K, which is to the best of our knowledge the first observation of a stepwise amorphous-amorphous-amorphous transformation sequence. We infer that the relation of HDA and VHDA is very similar to the relation between LDA and HDA except for a higher activation barrier between the former. We discuss the two options of thermodynamic versus kinetic origin of the phenomenon.     

Determination of selenium species in plant leaves by HPLC-UV-HG-AFS

The purpose of this work was the development of a method for the determination of Se compounds in leaves of plants. Water-soluble Se compounds were extracted from samples by water. Enzymatic hydrolysis with the non-specific enzyme protease XIV was used for the release of Se compounds bound to proteins. Separation of Se species was made by ion exchange chromatography, using an anion exchange column for Se^IV, Se^VI and selenomethionine (SeMet), and a cation exchange column for selenomethylselenocysteine (SeMeSeCys) and selenocystine (SeCys₂). Columns were connected “on line” to a hydride generation atomic fluorescence spectrometer (HG-AFS) using a UV lamp between the separation and detection system. The repeatability of the results obtained by the developed method was under 15% (R.S.D.) for all Se species; the detection limit was 2-10 ng Se/g of supernatant. The accuracy was checked by comparison with some literature data for reference materials since there were no suitable certified reference materials available. The method was used for the determination of Se compounds in chicory (Cichorium intybus L.) leaves from plants which were cultivated aeroponically with elevated concentrations of Na₂SeO₄ for different periods. Se accumulated efficiently in chicory leaves; up to 480 μg/g after 41 days of exposure, mostly (64%) as Se^VI, i.e. in the form of Se added. Beside inorganic Se, in the extracts from enzyme hydrolysis we also found SeMet (4.2-8.4%) and SeMeSeCys (<DL−0.7%). Some unidentified peaks were also observed in the chromatograms of plant extracts.     

The Synthesis of Anatase TiO2 Nanoparticles by Solvothermal Method using Ionic Liquid as Additive

The solvothermal reactions of Ti(OiPr)₄ in alcohol using ionic liquid as additive were investigated. In the presence of [BMIM][Cl], [BMIM][Br], [BMIM][NTf₂], [BMIM][SO₃Me], [BMIM][SO₄Me], or [BMIM][OTf] (BMIM = 1‐Butyl‐3‐methylimidazolium), pure anatase nanoparticles were obtained. The controlled hydrolysis of Ti(OiPr)₄ in the presence of ionic liquids to form titanium oxo clusters plays a key role in the formation of anatase nanostructures, and ionic liquids can be repeatedly used to synthesise anatase nanoparticles. However, in the presence of [BMIM][PF₆], [BMIM]₂[Ti(OH)₆] was obtained by an anion exchange reaction.     

A superdirective array of phase shift sources

A superdirective array of audio drivers is described, which is compact compared with the acoustic wavelength over some of its frequency range. In order to minimize the overall sound power output, and hence reduce the excitation of the reverberant field when used in an enclosed space, the individual drivers are made directional by using phase shift enclosures. The motivating application for the array is the enhancement of sound from a television, in a particular region of space, to aid hearing impaired listeners. The design is initially investigated, using free-field simulations, by comparing the performance of 8 monopoles, 8 phase shift loudspeakers, and a double array of 16 monopoles, with a contrast maximization formulation. The construction and testing of an array of 8 drivers is then discussed, together with its measured response in an anechoic environment. The result of using acoustic contrast maximization is then compared with a least squares formulation, which demonstrates that the performance of the least squares solution can be made similar to that given by acoustic contrast maximization in this application, with a suitable choice of the target field.     

Polylactides - synthesis,characterization and medical application

Polymerizations of lactides via cationic, anionic, and insertion mechanisms are described. The usefulness of these three mechanisms for preparative purposes is evaluated. The polymerization mechanisms initiated by Al-alkoxides or Sn(II)-2-ethylhexanoate are discussed in more detail. Furthermore, the usefulness of ¹³C NMR spectroscopy for the sequence analysis of copolylactones is demonstrated. Copolyesters of D,L-lactide and ϵ-caprolactone with T_g's around 35°C and high transparency were synthesized. Films of these copolylactones were characterized by various methods and their usefulness as resorbable wound dressing was evaluated. More than 30 patients were successfully treated with this novel wound dressings.     

Anionic and pseudoanionic polymerization of lactones - a comparison

Polymerization via anionic mechanisms or insertion mechanisms (pseudoanionic mechanisms) are compared for β-lactones and L-lactide. The following aspects are discussed: initiation and deprotonation of β-lactones, back-biting degradation, stereosequences of poly(β-D,L-butyrolactone), racemization of L-lactide, systematic variation of endgroups including synthesis of macromers.     

Beitrag zum röntgenographischen Nachweis von Phasen mit geringen Volumenanteilen

Following quantum counting statistical considerations relations were derived which enable to estimate the error of integral intensity measurements of weak interferences and the minimal detectable volume parts of minority phases as a function of the measuring conditions and of the given error limits, and to optimize the choice of radiation and monochromatization conditions for the X-ray analysis of minority phases.     

f-block MOFs: A Pathway to Heterometallic Transuranics

A novel series of heterometallic f-block-frameworks including the first examples of transuranic heterometallic ²³⁸U/²³⁹Pu-metal–organic frameworks (MOFs) and a novel monometallic ²³⁹Pu-analog are reported. In combination with theoretical calculations, we probed the kinetics and thermodynamics of heterometallic actinide(An)-MOF formation and reported the first value of a U-to-Th transmetallation rate. We concluded that formation of uranyl species could be a driving force for solid-state metathesis. Density of states near the Fermi edge, enthalpy of formation, band gap, proton affinity, and thermal/chemical stability were probed as a function of metal ratios. Furthermore, we achieved 97 % of the theoretical maximum capacity for An-integration. These studies shed light on fundamental aspects of actinide chemistry and also foreshadow avenues for the development of emerging classes of An-containing materials, including radioisotope thermoelectric generators or metalloradiopharmaceuticals.